[Ga2Cl4(dioxane)2]x: molecular structure and reactivity of a polymeric gallium(II) halide containing two five-coordinate gallium atoms about a Ga–Ga bond

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Pingrong Wei, Xiao-Wang Li and Gregory H. Robinson


Abstract

A polymeric 1,4-dioxane adduct of gallium(II) chloride, [Ga2Cl4(dioxane)2]x, containing two five-coordinate gallium atoms about a Ga–Ga bond [Ga–Ga 2.3825(9) Å], reacts with 1,4-dilithiotetraphenylbutadiene affording an unusual Ga(II)–tetraphenylbutadiene complex.


References

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  4. Inside the drybox (M. Braun Labmaster130) Ga2Cl4(Aldrich Chemical Co.)(17.8 mmol, 5 g) was dissolved in 1,4-dioxane (25 mL). The resulting mixture was filtered and the solution was allowed to stand at room temperature for several days resulting in colorless cubic crystals (4 g, 62% yield). Mp 158–159 °C. Anal. (E + R Microanalytical Laboratories, Parispanny, NY) Calc. (found) Ga2Cl4(dioxane)2: C, 21.00 (21.17); H, 3.50 (2.90%). The less than ideal hydrogen analysis may be due to the loosely associated solvent molecules. 1H NMR (300 MHz, 298 K, THF-d8): δ 3.52 (m, 2H, –OCH2); 13C NMR (300 MHz, 298 K, THF-d8): δ72.7 (–OCH2).
  5. A suspension of 1,4-dilithiotetraphenylbutadiene in diethyl ether (50 mL), obtained from reaction of diphenylacetylene (Aldrich Chemical Co.)(10 mmol, 1.78 g) and lithium (10 mmol, 0.071 g), was added to a diethyl ether solution of I(2.5 mmol, 1.14 g) at –78 °C. After stirring for 3 h at –78 °C, the system was allowed to slowly warm to room temperature, stirring continued overnight. The resulting solution was separated from the precipitate by filtration, and concentrated to about a half of its volume, and then kept at –20 °C for several days. Yellow crystals were obtained (1.0 g, 31%). Mp 92 °C. Anal. Calc. (found) Ph4C4GaCl2Li2(Et2O)3: C, 65.50 (65.07); H, 6.82 (6.54%). 1H NMR (300 MHz, 298 K, THF-d8): δ 1.07 (m, 18H, –OCH2CH3), 3.35 (m, 12H, –OCH2CH3), 6.68–7.15 (br, m, 20H, Ph H); 13CNMR (300 MHz, 298 K, THF-d8): δ 15.7 (–OCH2CH3), 66.3 (–OCH2CH3), 123.7, 125.1, 127.4, 127.5, 130.2, 131.5, 141.6, 143.6, 148.8, 149.6.
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